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Cyanide Linkage Isomerization Induced by Cobalt Oxidation-State Changes at a Co-Fe Prussian-Blue Analogue/ZnO
Ratnadip De1,2, Marius Hermesdorf3,4, Anupam Bera1,2
1Department of Functional Interfaces, Leibniz Institute of Photonic Technology, Albert-Einstein-Strasse 9, 07745, Jena, Germany.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|August 14, 2024
Summary
We discovered cyanide linkage isomerism in cobalt-iron Prussian blue analogue/zinc oxide (PBA/ZnO) electrodes, influenced by fabrication temperature. This finding offers a new way to control interfacial composition for electrochemical applications.
Area of Science:
- Materials Science
- Electrochemistry
- Surface Chemistry
Background:
- Understanding interfacial composition in heterostructures is key for optimizing electrochemical and photoelectrochemical processes.
- Prussian blue analogues (PBAs) are versatile materials for energy applications, but their interfacial behavior needs further elucidation.
Purpose of the Study:
- To investigate the interfacial structure of cobalt-iron Prussian blue analogue modified zinc oxide (PBA/ZnO) electrodes.
- To understand the influence of fabrication temperature on interfacial composition and properties.
Main Methods:
- Vibrational sum frequency generation (VSFG) spectroscopy, including in situ spectro-electrochemistry.
- Photoluminescence spectroscopy.
- X-ray photoelectron spectroscopy (XPS).
Main Results:
- First observation of cyanide linkage isomerism at the PBA/ZnO interface, dependent on fabrication temperature.
- Correlation of Co(II)→Co(III) oxidation with a CN ligand flip from Co-NC-Fe to Co-CN-Fe coordination.
- Identification of surface defects on ZnO acting as oxidation sites for PBA, linked to fabrication temperature.
Conclusions:
- The study reveals an interplay between ZnO surface states and PBA composition.
- Fabrication temperature controls surface defects, influencing interfacial linkage isomerism.
- This offers a method to tune interfacial chemical composition for tailored applications.
Keywords:
Co−Fe Prussian Blue-ZnOHybrid heterostructureInterfacial engineeringLinkage isomerizationVSFG spectroscopyMore Related Videos
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